Near-IR emitting lanthanide chelates are of increasing interest as biological imaging agents as a consequence of the transparency of biological tissue to near-IR radiations coupled with the fact that low energy absorbing chromophores can be used to sensitise near-IR lanthanide based emission. Metal complexes containing polypyridine ligands have low energy ³MLCT states suitable for populating the emissive states of near-IR emitting lanthanide ions. This thesis describes the synthesis and photophysical properties of a series of kinetically stable lanthanide complexes covalently linked to transition metal complexes.

Lanthanide luminescence and in particular sensitised emission from both europium (III) and terbium (III) is reviewed. The use of both europium and terbium as biological markers is covered, concentrating on time-resolved fluoroimmunoassays (TR-FIA), and more recently nucleic acid hybridisation assays. A new approach is described for the design of cooperative ligands that enhance europium luminescence in aqueous solution. This involves a three-component system comprised of the europium. ion, a sensitising ligand, 1,10-Phenanthroline-2,9- biscarboxylic acid, and a separate non-sensitising ligand, N-(butylacetamido)- ethyl enediamine-N, N, N'-tri acetate. The synthesis of a novel class of europium sensitiser is described 5-(Hexanoylphenanthridinium)-2,9-biscarboxylic acid- 1,1 O-phenanthroline. A homogeneous method for identifying the presence of a single strand of DNA is described which employs 5-(Hexanoylphenanthridinium)-2,9-biscarboxylic acid- ,10- phenanthroline as a cooperative sensitiser of europium (M) luminescence.

This work presents the results of an investigation into the technique of combined TEM-Cathodoluminescence and its application to the study of GaN epitaxial layers grown by MOVPE and PAMBE on sapphire and LiAlO(_2) substrates respectively - and MOVPE grown In(_x)Ga(_1-x)N/GaN/A1(_2)O(_3) QW structures. The measurement of CL in a TEM allows spectral information to be correlated with structural information. In-situ electron beam degradation curves of panchromatic CL from GaN epilayers and In(_0.1)Ga(_0.9)N QW emission revealed a decline in the luminescence which could be attributed to the introduction of non-radiative recombination centres. The influence of thickness on both CL spectra and images was investigated experimentally and by modelling. A method of normalising STEM-CL images for thickness contrast was developed. Application of this normalisation to In(_0.1)Ga(_0.9)N QWs in cross-section revealed inhomogeneous CL with bright regions 200-700nm in width. No systematic relationship was identified between luminescence at the QW peak emission wavelength, QW(_A), and luminescence at QW(_A) ±10nm. This finding does not support the hypothesis that variation in QW CL brightness is due to local compositional fluctuation. However, clusters of threading dislocations were shown to suppress QW luminescence and are suggested as a cause for the observed inhomogeneity in luminescence. A statistical analysis of (dislocation related) V-pits in In(_x)Ga(_1-x)N MQW samples revealed clustering of pits on a length scale of 60-120nm, but no long range clustering indicative of sub-grain boundaries was found. Finally TEM-CL spectra and monochromatic line-scans were used to show that bundles of basal plane stacking faults in M-plane GaN epitaxial layers grown on LiAlO(_2) emit radiatively at 3.3-3.35eV (l00K). The radiative transition energy is consistent with models in the literature that consider basal plane stacking faults to be layers of cubic GaN in the wurtzite matrix which act as type II QWs.

Dated 1983 / Bibliography: leaves xxii-xxxii / 194, xxxii leaves : ill. ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.)--University of Adelaide, Dept. of Physics, 1964

`Revised figures` (21 leaves) in pocket / Bibliography: leaves i-xv / 126, xv leaves, [2] leaves of plates : ill ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.)--University of Adelaide, Dept. of Physics, 1987

Bibliography: leaves 120-127 / iv, 127, [158] leaves : ill., map ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.)--University of Adelaide, Dept. of Physics and Mathematical Physics, 1990

Depuis le début des années 2000, les performances des diodes électroluminescentes (LED) ne cessent de s’améliorer alors que leur prix connait une diminution spectaculaire grâce à une production à grande échelle liée au marché de l'éclairage. Ainsi, les LED deviennent une source de lumière intéressante pour le pompage de lasers solides, intermédiaire entre les lampes flash et les diodes laser. C’est pourquoi, nous proposons dans cette thèse, de revisiter le pompage laser par LED, 40 ans après la première démonstration. Nous avons démontré le premier système laser Nd:YVO4 pompé directement par LED. La brillance des LEDs limitant fortement les performances, nous nous sommes intéressé au concept de concentrateur luminescent (en Ce:YAG) pompé par LED. Nous avons ainsi développé une nouvelle source d’éclairage haute brillance, améliorant les performances des LEDs d’un facteur 20 pour aboutir à des éclairements comparables à ceux des diodes laser (de l’ordre de plusieurs kW/cm²). Le pompage laser par cette nouvelle source de pompage a été validé pour la première fois sur les cristaux laser de Nd:YVO4 (3 mJ obtenus avec un profil monomode et 6 mJ en multimode) ainsi que sur des cristaux de Nd:YAG. Dans ce dernier cas, un déclenchement passif à l’aide d’absorbants saturables a permis d'obtenir ainsi des performances encore jamais atteintes pour un laser pompé par LED. Ainsi, les concentrateurs pompés par LED ouvrent de nouvelles possibilités pour le pompage de matériaux laser nécessitant de forte brillance de pompage. Les premiers essais sur le saphir dopé au titane montrent qu'il est possible d'obtenir du gain sur ce matériau en pompage par LED. / Since the early 2000s, the lighting market is constantly growing up, pulling the Light-Emitting Diodes (LED) performance forward and pushing their cost down. LED is becoming an interesting source of light for laser pumping, between flashlamp and laser diodes. Thus, 40 years after the first demonstration, we suggest to revisit laser LED pumping. In this work, we demonstrated for the first time a Nd:YVO4 laser directly LED-pumped. LED radiance being limited, we took interest in LED-pumped luminescent concentrators. By developing Ce:YAG concentrator, we were able to overcome the LEDs irradiance by a factor of 20, leading to output irradiances similar to the laser diode ones (of the order of multi-kW/cm²). We validated the concept by pumping for the first time a Nd:YVO4 crystal and a Nd:YAG crystal with luminescent concentrators. Output energies of several mJ were obtained. In addition, we succeeded to get a passively Q-switched regime for the Nd:YAG laser by using saturable absorbers leading to unpreceded performance for a LED-pumped laser. Finally, LED-pumped concentrators pave the way for new possibilities for high-radiance source pumped media. Our first tests on titanium doped sapphire show that a laser gain with a LED pumping is achievable.

Dans ce travail de these, nous étudions comment des nano-structures métalliques modifient le processus d'émission spontannée d'objets fluorescents et jouent ainsi un rôle d'antenne. Ces structures supportent des modes optiques confinés aux interfaces metal-diélectrique: ce sont des modes plasmoniques.De par leur fort confinement, ces modes modifient la densité locale d'états optiques et permettent notamment d'accélérer le processus d'émission spontannée (facteur de Purcell). Nous étudions le cas d'une structure planaire metal-isolant-métal de type patch couplée à un ensemble de nanocristaux colloïdaux fluorescents. Nos mesures, soutenues par des calculs numériques, montrent une acceleration de l'émission fluorescente d'un facteur 80 ainsi qu'une augmentation de la directivité de l'émission. Nous décrivons ensuite le procedé de fabrication d'une structure patch metal-semiconducteur-métal pour laquelle la source fluorescente est un puits quantique émettant dans le proche infra-rouge. Nous montrons que l'antenne permet d'augmenter l'extraction fluorescente d'un facteur 8. Enfin, nous considérons le cas d'une structure sphérique composée d'un unique nanocristal fluorescent au centre d'une bille de silice entourée par une fine coquille métallique. Cette structure plasmonique accélère l'émission d'une facteur 10 et permet de supprimer le scintillement caractéristique de l'émission des nanocristaux. La coquille métallique permet également d'isoler chimiquement le nanocristal de l'environnement, assurant ainsi une grande photostabilité et une toxicité réduite. L'émetteur ainsi obtenu est donc un candidat prometteur pour des applications de marquage de fluorescence in-vivo. / The present work focuses on the modification of spontaneous emission of fluorescent emitters using metallic nano-structures. These structures support confined plasmonic modes that strongly increase the local density of optical states. Consequently, the plasmonic structure enhances the spontaneous decay rate of the emitter. We use both numerical simulations and experimental results to demonstrate the potential of plasmonic antennas as tools to control spontaneous emission. First, we study a metal-dielectric-metal planar structure called patch antenna. This structure is coupled to an ensemble of quantumdots emitting visible light. We show that, in the presence of the patch antenna, the fluorescent emission is accelerated by a factor 80 and that its directivity is increased. Then, we use a similar plasmonic structure coupled to a quantum well emitting in the near infrared. Using an ad hoc hyperspectral imaging setup, we show that the antenna increases the extracted light by a factor 8. Finally, we study a spherical geometry composed of a single fluorescent quantum dot at the center of a silica bead coated with a thin gold shell. This plasmonic structure

Το αντικείμενο της παρούσας Διδακτορικής Διατριβής είναι η αλληλεπίδραση της ηλεκτρομαγνητικής ακτινοβολίας με νανοδομημένους ημιαγωγούς. Για το σκοπό αυτό σχεδιάστηκε και κατασκευάστηκε μια διάταξη καταγραφής φασμάτων φωτοφωταύγειας, συναρτήσει της θερμοκρασίας. Τα δείγματα που εξετάστηκαν περιέχουν νανοκρυστάλλους του πυριτίου. Ερευνήθηκαν δυο διαφορετικές προσεγγίσεις για την παρασκευή τέτοιων δειγμάτων. Η πρώτη αφορά την θερμική αποσύνθεση του SiO σε θερμοκρασίες άνω των 850 ºC και οδηγεί στην παρασκευή δειγμάτων με νανοκρυστάλλους πυριτίου σε μια μήτρα από οξείδιο του πυριτίου. Η δεύτερη είναι ο σχηματισμός πορώδους πυριτίου μέσω ανοδικής ηλεκτροδιάβρωσης, τόσο σε συνθήκες ανοδικής πόλωσης, όσο και σε συνθήκες ανοιχτού κυκλώματος. Τα δείγματα που προήλθαν από θερμική αποσύνθεση του SiO επιδεικνύουν έντονη φωτοφωταύγεια, σε θερμοκρασία περιβάλλοντος, στο εγγύς υπέρυθρο και σε ενέργειες μεγαλύτερες του ενεργειακού χάσματος του πυριτίου (1.12 eV), ως αποτέλεσμα της εξιτονικής επανασύνδεσης υπό συνθήκες κβαντικού εντοπισμού. Τα φάσματα φωτοφωταύγειας και ο δομικός χαρακτηρισμός, έδωσαν χρήσιμες πληροφορίες σχετικά με την αλληλεπίδραση και προέλευση της εκπεμπόμενης ακτινοβολίας, της δομής και κινητικής του SiO που υπόκειται σε θερμική αποσύνθεση. Με την παρασκευή πορώδους πυριτίου, αναπτύχθηκε μια νέα μεθοδολογία για την ανάπτυξη μικροδομών πορώδους πυριτίου σε συνθήκες ανοιχτού κυκλώματος, με απολύτως ελεγχόμενη γεωμετρία και ιδιότητες φωτοφωταύγειας. Η μεθοδολογία αυτή είναι ενδιαφέρουσα για την ανάπτυξη μιας πληθώρας μικρο-ηλεκτρομηχανικών συστημάτων βασισμένα στο πορώδες πυρίτιο, όπως οπτοηλεκτρονικές διατάξεις και αισθητήρες. / The objective of this Thesis is the study of the interaction of electromagnetic radiation with nanostructured semiconductors. For this purpose we have designed and constructed a photoluminescence setup for the recording of spectra at various temperatures. The samples that have been investigated contain nanocrystals of silicon. We investigated two different approaches for the synthesis of such samples. The first one involves the thermal decomposition of SiO at temperatures above 850 ºC and results in silicon nanocrystals embedded in silicon oxide matrix. The second is the formation of porous silicon using the anodic dissolution of silicon under external anodic bias, as well as under open circuit potential conditions. Samples prepared by thermal decomposition of SiO exhibit strong photoluminescence, at room temperature, in the near infrared and at energies higher than the band gap of bulk silicon (1.12 eV), as a result of excitonic recombination under quantum confinement conditions. The recorded spectra and the structural characterization, gave us valuable information about the interaction, the origin of the emitted radiation, the structure and the kinetics of SiO undergoing thermal decomposition. The investigations concerning the formation of porous silicon, resulted in the development of a novel technique for the formation of porous silicon microstructures under open circuit potential conditions. The microstructure geometry and photoluminescence characteristics can be tuned. This technique is interesting for the fabrication of a variety of micro-electromechanical systems, based on porous silicon, such as optoelectronic devices and sensors.

Un-doped, Tb3+ as well as Yb3+ doped ZnO nanocrystals with different concentrations of RE3+ (Tb3+, Yb3+) ions were successfully synthesized via sol-gel method to produce rare earth activated zinc oxide nanophosphors. The phosphor powders were produced by drying the precursor gels at 200˚C in ambient air. Based on the X-ray diffraction results, it was found that the pure and RE3+ doped ZnO nanophosphors were highly polycrystalline in nature regardless of the incorporation of Tb3+ or Yb3+ ions. Moreover, the diffraction patterns were all indexed to the ZnO Hexagonal wurtzite structure and belong to P63mc symmetry group. The Raman spectroscopy confirmed the wurtzitic structure of the prepared samples. Elemental mapping conducted on the as prepared samples using Scanning electron microscope (SEM) equipped with energy dispersive X-ray spectrometer (EDX) revealed homogeneous distribution of Zn, O, and RE3+ ions. The high resolution transmission electron microscope (HR-TEM) analyses indicated that the un-doped and RE3+ doped samples were composed of hexagonal homogeneously dispersed particles of high crystallinity with an average size ranging from 4 to 7 nm in diameter, which was in agreement with X-ray diffraction (XRD) analyses. ZnO:Tb3+ PL study showed that among different Tb3+ concentrations, 0.5 mol% Tb3+ doped ZnO nanoparticles showed clear emission from the dopant originating from the 4f-4f intra-ionic transitions of Tb3+ while the broad defects emission was dominating in the 0.15 and 1 mol% Tb3+doped ZnO. Optical band-gap was extrapolated from the Ultraviolet Visible spectroscopy (UV-Vis) absorption spectra using TAUC‟s method and the widening of the optical band-gap for the doped samples as compared to the un-doped sample was observed. The PL study of ZnO:Yb3+ samples was studied using a 325 nm He-Cd laser line. It was observed that the ZnO exciton peak was enhanced as Yb3+ions were incorporated in ZnO matrix. Furthermore, UV-VIS absorption spectroscopic study revealed the widening of the band-gap in Tb3+ doped ZnO and a narrowing in the case of Yb3+ doped ZnO system. X-ray photoelectron spectroscopy demonstrated that the dopant was present in the doped samples and the result was found to be consistent with PL data from which an energy transfer was evidenced. Energy transfer mechanism was evidenced between RE3+ and ZnO nanocrystals and was discussed in detail. / Physics / M.Sc. (Physics)